JPH0557975B2 - - Google Patents
Info
- Publication number
- JPH0557975B2 JPH0557975B2 JP59005525A JP552584A JPH0557975B2 JP H0557975 B2 JPH0557975 B2 JP H0557975B2 JP 59005525 A JP59005525 A JP 59005525A JP 552584 A JP552584 A JP 552584A JP H0557975 B2 JPH0557975 B2 JP H0557975B2
- Authority
- JP
- Japan
- Prior art keywords
- methylpropyl
- methylpropyl chloride
- chloride
- alkoxyphenyl
- chloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- QTBFPMKWQKYFLR-UHFFFAOYSA-N isobutyl chloride Chemical compound CC(C)CCl QTBFPMKWQKYFLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- -1 phenoxybenzyl Chemical group 0.000 description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CUYNTLDCNGKIFN-UHFFFAOYSA-N 1-(1-chloro-2-methylpropan-2-yl)-4-ethoxybenzene Chemical compound CCOC1=CC=C(C(C)(C)CCl)C=C1 CUYNTLDCNGKIFN-UHFFFAOYSA-N 0.000 description 5
- BSPCSKHALVHRSR-UHFFFAOYSA-N 2-chlorobutane Chemical compound CCC(C)Cl BSPCSKHALVHRSR-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- FISWUVUAFGHPHT-UHFFFAOYSA-N 2-chloro-4-(1-chloro-2-methylpropan-2-yl)-1-ethoxybenzene Chemical compound CCOC1=CC=C(C(C)(C)CCl)C=C1Cl FISWUVUAFGHPHT-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000005224 alkoxybenzenes Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- HIVHNLGXPXJFRW-UHFFFAOYSA-N 1-(1-chloro-2-methylpropan-2-yl)-4-methoxybenzene Chemical compound COC1=CC=C(C(C)(C)CCl)C=C1 HIVHNLGXPXJFRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- IQDNKGZULJFFIO-UHFFFAOYSA-N 1-(1-chloro-2-methylpropyl)-2-methoxybenzene Chemical compound COC1=CC=CC=C1C(Cl)C(C)C IQDNKGZULJFFIO-UHFFFAOYSA-N 0.000 description 1
- KWISWUFGPUHDRY-UHFFFAOYSA-N 1-Chloro-2-methylpropene Chemical compound CC(C)=CCl KWISWUFGPUHDRY-UHFFFAOYSA-N 0.000 description 1
- FUMQKSSYCBTBRD-UHFFFAOYSA-N 2-bromo-4-(1-chloro-2-methylpropan-2-yl)-1-ethoxybenzene Chemical compound CCOC1=CC=C(C(C)(C)CCl)C=C1Br FUMQKSSYCBTBRD-UHFFFAOYSA-N 0.000 description 1
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229960004109 potassium acetate Drugs 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は２−（４−アルコキシフエニル）−２−
メチルプロピピルクロリド類の製造法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides 2-(4-alkoxyphenyl)-2-
This invention relates to a method for producing methylpropyl chloride.
更に詳しくは、一般式（）；
（式（）中、Ｒは低級アルキル基を表わし、
Ｘは塩素原子、臭素原子を表わす）で表わされる
２−（３−ハロゲノ−４−アルコキシフエニル）−
２−メチルプロピルクロリド類を、塩基の存在
下、パラジウム触媒、白金触媒あるいはニツケル
触媒の存在下、接触還元により脱ハロゲン化する
ことを特徴とする一般式（）；
（式（）中、Ｒは前記の意味を表わす）で表
わされる２−（４−アルコキシフエニル）−２−メ
チルプロピルクロリド類の製造法に関する。２−
（４−アルコキシフエニル）−２−メチルプロピル
クロリド類は各種産業分野において有用な化合物
であり、農薬とりわけ殺虫剤の中間体として有用
である。 More specifically, the general formula (); (In formula (), R represents a lower alkyl group,
2-(3-halogeno-4-alkoxyphenyl)- represented by
General formula () characterized in that 2-methylpropyl chloride is dehalogenated by catalytic reduction in the presence of a base, a palladium catalyst, a platinum catalyst, or a nickel catalyst; The present invention relates to a method for producing 2-(4-alkoxyphenyl)-2-methylpropyl chloride represented by the formula (in which R represents the above meaning). 2-
(4-Alkoxyphenyl)-2-methylpropyl chlorides are useful compounds in various industrial fields, and are particularly useful as intermediates for pesticides.
２−（４−アルコキシフエニル）−２−メチルプ
ロピルクロリド類は高い殺虫、殺ダニ活性を有
し、速効性、残効性および低魚毒性において優れ
た特徴を有する新規殺虫剤である３−フエノキシ
ベンジル２−（４−アルコキシフエニル）−２−メ
チルプロピルエーテル類（特開昭57−72928号公
報、特開昭57−64632号公報）の重要な中間体で
ある。２−（４−アルコキシフエニル）−２−メチ
ルプロピルクロリド類を製造する方法として、ア
ルコキシベンゼン類と３−クロロ−２−メチル−
１−プロペンとから製造する方法がある。 2-(4-Alkoxyphenyl)-2-methylpropyl chloride is a new insecticide that has high insecticidal and acaricidal activity, and has excellent characteristics in terms of fast-acting, residual effect, and low toxicity to fish. It is an important intermediate of phenoxybenzyl 2-(4-alkoxyphenyl)-2-methylpropyl ethers (JP-A-57-72928, JP-A-57-64632). As a method for producing 2-(4-alkoxyphenyl)-2-methylpropyl chloride, alkoxybenzenes and 3-chloro-2-methyl-
There is a method of producing it from 1-propene.
たとえば、濃硫酸の存在下、アニソールと３−
クロロ−２−メチル−１−プロペンを反応させ２
−（４−メトキシフエニル）−２−メチルプロピル
クロリドを合成する方法が報告されている
（Chem.Ber.，94，2609（1961））。この方法では、
目的の２−（４−メトキシフエニル）−２−メチル
プロピルクロリドが同時に生成する異性体２−
（２−メトキシフエニル）−２−メチルプロピルク
ロリドの３割から５割程度しか生成しないため精
密な蒸留操作等が必要である。また、アニソール
以外の他のアルコキシベンゼン類においても同様
の結果を与えることが予想される。 For example, in the presence of concentrated sulfuric acid, anisole and 3-
React chloro-2-methyl-1-propene 2
A method for synthesizing -(4-methoxyphenyl)-2-methylpropyl chloride has been reported (Chem. Ber., 94 , 2609 (1961)). in this way,
The desired 2-(4-methoxyphenyl)-2-methylpropyl chloride is produced simultaneously with isomer 2-
Since only about 30% to 50% of (2-methoxyphenyl)-2-methylpropyl chloride is produced, precise distillation operations are required. Furthermore, it is expected that other alkoxybenzenes other than anisole will give similar results.
従つて、アルコキシベンゼン類と３−クロロ−
２−メチル−１−プロペンを出発原料として目的
の２−（４−アルコキシフエニル）−２−メチルプ
ロピルクロリドを工業的に製造することは非常に
不利である。 Therefore, alkoxybenzenes and 3-chloro-
It is very disadvantageous to industrially produce the desired 2-(4-alkoxyphenyl)-2-methylpropyl chloride using 2-methyl-1-propene as a starting material.
その他の方法として、特開昭58−88336号公公
報には２−（４−アシルオキシフエニル）−２−メ
チルプロピルクロリド類を塩基及びアルキル化剤
と処理し、２−（４−アルコキシフエニル）−２−
メチルプロピルクロリド類を製造する方法が報告
されている。 As another method, JP-A No. 58-88336 discloses that 2-(4-acyloxyphenyl)-2-methylpropyl chloride is treated with a base and an alkylating agent, and 2-(4-alkoxyphenyl) )-2-
A method for producing methylpropyl chloride has been reported.
しかしながら、この方法で用いられる出発原料
の２−（４−アシルオキシフエニル）−２−メチル
プロピルクロリド類の製造には４−ｔ−ブチルフ
エノールをアシル化し、さらに光塩素化（特開昭
58−83650号公報）する二工程が必要である上に、
光塩素化工程の反応混合物からの原料の分離、生
成した副生物の分離などのために精密な蒸留操作
等の複雑な精製工程を必要とするなど工業的に非
常に不利である。 However, in order to produce 2-(4-acyloxyphenyl)-2-methylpropyl chloride, which is the starting material used in this method, 4-t-butylphenol is acylated and then photochlorinated (as described in
58-83650)).
This method is very disadvantageous industrially, as it requires complex purification steps such as precise distillation operations in order to separate raw materials from the reaction mixture in the photochlorination step and to separate generated by-products.
この様なことから２−（４−アルコキシフエニ
ル）−２−メチルプロピルクロリド類を容易に製
造する工業的方法が望まれていた。 For these reasons, an industrial method for easily producing 2-(4-alkoxyphenyl)-2-methylpropyl chlorides has been desired.
本発明者らは２−（４−アルコキシフエニル）−
２−メチルプロピルクロリド類の工業的に有利な
製造方法について鋭意検討した結果驚くべきこと
に２−（３−ハロゲノ−４−アルコキシフエニル）
−２−メチルプロピルクロリド類を塩基の存在
下、接触還元することにより２−（４−アルコキ
シフエニル）−２−メチルプロピルクロリド類が
高収率で選択的に得られることを見出し、本発明
を完成した。 The inventors have determined that 2-(4-alkoxyphenyl)-
As a result of intensive studies on industrially advantageous production methods for 2-methylpropyl chlorides, it was surprisingly found that 2-(3-halogeno-4-alkoxyphenyl)
It has been discovered that 2-(4-alkoxyphenyl)-2-methylpropyl chloride can be selectively obtained in high yield by catalytic reduction of -2-methylpropyl chloride in the presence of a base, and the present invention completed.
本発明により製造される２−（４−アルコキシ
フエニル）−２−メチルプロピルクロリド類は一
般式（）；
で表わされる。 The 2-(4-alkoxyphenyl)-2-methylpropyl chloride produced by the present invention has the general formula (); It is expressed as
式（）中、Ｒは低級アルキル基を表わし、具
体的にはメチル基、エチル基、ｎ−プロピル基、
イソプロピル基、ｎ−ブチル基、イソブチル基、
ｔ−ブチル基、ｎ−ペンチル基、イソペンチル
基、ネオペンチル基、ｔ−ペンチル基、ｎ−ヘキ
シル基、イソヘキシル基などを表わす。これらの
２−（４−アルコキシフエニル）−２−メチルプロ
ピルクロリド類としては２−（４−メトキシフエ
ニル）−２−メチルプロピルクロリド、２−（４−
エトキシフエニル）−２−メチルプロピルクロリ
ド、２−（４−ｎ−プロポキシフエニル）−２−メ
チルプロピルクロリド、２−（４−イソプロポキ
シフエニル）−２−メチルプロピルクロリド、２
−（４−ｎ−ブトキシフエニル）−２−メチルプロ
ピルクロリド、２−（４−ｔ−ブトキシフエニル）
−２−メチルプロピルクロリド、２−（４−ｎ−
ペンチルオキシフエニル）−２−メチルプロピル
クロリド、２−（４−イソペンチルオキシフエニ
ル）−２−メチルプロピルクロリド、２−（４−ｎ
−ヘキシルオキシフエニル）−２−メチルプロピ
ルクロリドなどの上記アルキル基置換オキシフエ
ニル誘導体が挙げられる。 In formula (), R represents a lower alkyl group, specifically a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group,
Represents a t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, etc. These 2-(4-alkoxyphenyl)-2-methylpropyl chlorides include 2-(4-methoxyphenyl)-2-methylpropyl chloride, 2-(4-
ethoxyphenyl)-2-methylpropyl chloride, 2-(4-n-propoxyphenyl)-2-methylpropyl chloride, 2-(4-isopropoxyphenyl)-2-methylpropyl chloride, 2
-(4-n-butoxyphenyl)-2-methylpropyl chloride, 2-(4-t-butoxyphenyl)
-2-methylpropyl chloride, 2-(4-n-
pentyloxyphenyl)-2-methylpropyl chloride, 2-(4-isopentyloxyphenyl)-2-methylpropyl chloride, 2-(4-n
-hexyloxyphenyl)-2-methylpropyl chloride and the above alkyl group-substituted oxyphenyl derivatives.
本発明において原料として使用される２−（３
−ハロゲノ−４−アルコキシフエニル）−２−メ
チルプロピルクロリド類は式（）；
で表わされる。式（）中、Ｒは前記の低級アル
キル基を表わし、Ｘは塩素原子、臭素原子を表わ
す。これらの２−（３−ハロゲノ−４−アルコキ
シフエニル）−２−メチルプロピルクロリド類と
しては次の様な化合物が挙げられる。 2-(3) used as raw material in the present invention
-halogeno-4-alkoxyphenyl)-2-methylpropyl chloride has the formula (); It is expressed as In formula (), R represents the above-mentioned lower alkyl group, and X represents a chlorine atom or a bromine atom. Examples of these 2-(3-halogeno-4-alkoxyphenyl)-2-methylpropyl chlorides include the following compounds.
２−（３−クロロ−４−メトキシフエニル）−２
−メチルプロピルクロリド、２−（３−ブロモ−
４−メトキシフエニル）−２−メチル−プロピル
クロリド、２−（３−クロロ−４−エトキシフエ
ニル）−２−メチルプロピルクロリド、２−（３−
ブロモ−４−エトキシフエニル）−２−メチルプ
ロピルクロリド、２−（３−クロロ−４−ｎ−プ
ロポキシフエニル）−２−メチルプロピルクロリ
ド、２−（３−ブロモ−４−イソプロポキシフエ
ニル）−２−メチルプロピルクロリド、２−（３−
クロロ−４−ｎ−ブトキシフエニル）−２−メチ
ルプロピルクロリド、２−（３−ブロモ−４−イ
ソブトキシフエニル）−２−メチルプロピルクロ
リド、２−（３−クロロ−４−ｔ−ブトキシフエ
ニル）−２−メチルプロピルクロリド、２−（３−
ブロモ−４−ｎ−ブトキシフエニル）−２−メチ
ルプロピルクロリド、２−（３−クロロ−４−イ
ソペンチルオキシフエニル）−２−メチルプロピ
ルクロリド、２−（３−ブロモ−４−ｎ−ヘキシ
ルオキシフエニル）−２−メチルプロピルクロリ
ドなどが挙げられる。 2-(3-chloro-4-methoxyphenyl)-2
-Methylpropyl chloride, 2-(3-bromo-
4-methoxyphenyl)-2-methyl-propyl chloride, 2-(3-chloro-4-ethoxyphenyl)-2-methylpropyl chloride, 2-(3-
Bromo-4-ethoxyphenyl)-2-methylpropyl chloride, 2-(3-chloro-4-n-propoxyphenyl)-2-methylpropyl chloride, 2-(3-bromo-4-isopropoxyphenyl) )-2-methylpropyl chloride, 2-(3-
Chloro-4-n-butoxyphenyl)-2-methylpropyl chloride, 2-(3-bromo-4-isobutoxyphenyl)-2-methylpropyl chloride, 2-(3-chloro-4-t-butoxyphenyl)- 2-methylpropyl chloride, 2-(3-
Bromo-4-n-butoxyphenyl)-2-methylpropyl chloride, 2-(3-chloro-4-isopentyloxyphenyl)-2-methylpropyl chloride, 2-(3-bromo-4-n-hexyloxy (phenyl)-2-methylpropyl chloride and the like.
出発原料の２−（３−ハロゲノ−４−アルコキ
シフエニル）−２−メチルプロピルクロリド類は
２−ハロゲノ−アルコキシベンゼン類と３−クロ
ロ−２−メチル−１−プロペンを酸触媒の存在下
反応させると容易に、かつ、選択的に製造でき
る。 The starting material 2-(3-halogeno-4-alkoxyphenyl)-2-methylpropyl chloride is obtained by reacting 2-halogeno-alkoxybenzene and 3-chloro-2-methyl-1-propene in the presence of an acid catalyst. By doing so, it can be easily and selectively manufactured.
本発明の製造法において使用される触媒として
はロジウム触媒、ルテニウム触媒、レニウム触
媒、パラジウム、パラジウムカーボンなどのパラ
ジウム触媒、酸化白金、白金カーボンなどの白金
触媒、ラネーニツケル、還元ニツケル、蟻酸ニツ
ケル、漆原ニツケル、ニツケル−銅などのニツケ
ル触媒、銅クロム酸化物などの銅触媒等の接触還
元触媒が挙げられ、中でもパラジウム触媒、白金
触媒、ニツケル触媒が良く、好ましくはパラジウ
ム触媒であり、より好ましくはパラジウムカーボ
ンであり、塩基としては水酸化ナトリウム、水酸
化カリウム、水酸化カルシウムなどのアルカリ金
属及びアルカリ土類金属の水酸化物類、炭酸ナト
リウム、炭酸水素ナトリウム、炭酸カリウムなど
の炭酸塩類、リン酸三ナトリウムなどのリン酸塩
類、ギ酸ナトリウム、酢酸ナトリウム、酢酸カリ
ウム、酢酸マグネシウム、プロピオン酸ナトリウ
ムなどの有機酸塩類、酸化マグネネシウム、酸化
カルシウムなどのアルカリ土類金属の酸化物類、
ピリジン、トリエチルアミンなどの有機塩基類等
があり、好ましくは酢酸塩類である。 Catalysts used in the production method of the present invention include rhodium catalysts, ruthenium catalysts, rhenium catalysts, palladium, palladium catalysts such as palladium carbon, platinum catalysts such as platinum oxide and platinum carbon, Raney nickel, reduced nickel, nickel formate, and urushihara nickel. , nickel catalysts such as nickel-copper, and copper catalysts such as copper chromium oxide. Among them, palladium catalysts, platinum catalysts, and nickel catalysts are preferable, and palladium catalysts are preferable, and palladium carbon is more preferable. The bases include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, and calcium hydroxide, carbonates such as sodium carbonate, sodium bicarbonate, and potassium carbonate, and trisodium phosphate. phosphates, organic acid salts such as sodium formate, sodium acetate, potassium acetate, magnesium acetate, sodium propionate, alkaline earth metal oxides such as magnesium oxide, calcium oxide,
Examples include organic bases such as pyridine and triethylamine, and acetates are preferred.
不可欠なものではないが、収率の向上のため、
溶媒を使用した方が望ましい。溶媒としては水、
あるいはメタノール、エタノール、イソプロピル
アルコールなどのアルコール類、酢酸、プロピオ
ン酸などの有機酸類、ギ酸メチル、酢酸メチル、
酢酸エチル、酢酸イソプロピル、酢酸ブチルなど
のエステル類、ジエチルエーテル、テトラヒドロ
フラン、１，４−ジオキサンなどのエーテル類、
アセトン、メチルエチルケトンなどのケトン類、
ヘキサン、ヘプタンなどの脂肪族炭化水素類、ベ
ンゼン、トルエンなどの芳香族化合物類、Ｎ，Ｎ
−ジメチルホルムアミド、ジメチルイミダゾリジ
ノン、ヘキサメチルホスホルアミドなどの非プロ
トン性極性溶媒類などがあり、一種もしくは二種
以上混合して使用する。好ましくは酢酸エステル
類である。 Although not essential, to improve yield,
It is preferable to use a solvent. Water as a solvent,
Or alcohols such as methanol, ethanol, and isopropyl alcohol, organic acids such as acetic acid and propionic acid, methyl formate, methyl acetate,
Esters such as ethyl acetate, isopropyl acetate, butyl acetate, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane,
Ketones such as acetone and methyl ethyl ketone,
Aliphatic hydrocarbons such as hexane and heptane, aromatic compounds such as benzene and toluene, N,N
- There are aprotic polar solvents such as dimethylformamide, dimethylimidazolidinone, hexamethylphosphoramide, etc., which are used singly or in combination of two or more. Acetate esters are preferred.
水素圧は常圧ないし150Kg／cm2Ｇで、反応温度
は−20℃ないし100℃、好ましくは10℃ないし60
℃である。 The hydrogen pressure is normal pressure to 150 kg/cm 2 G, and the reaction temperature is -20°C to 100°C, preferably 10°C to 60°C.
It is ℃.
接触還元触媒は、２−（３−ハロゲノ−４−ア
ルコキシフエニル）−２−メチルプロピルクロリ
ド１部に対して0.00001部〜0.5部（金属換算）、
好ましくは0.0001〜0.2部、溶媒が必要な場合は
0.1〜30部、好ましくは1.0〜10部の溶媒を使用す
る。使用量が多い場合には生産性が低下する。塩
基は、２−（３−ハロゲノ−４−アルコキシフエ
ニル）−２−メチルプロピルクロリド１当量に対
して0.5〜10当量、好ましくは1.0〜2.0当量使用す
る。 The catalytic reduction catalyst is 0.00001 part to 0.5 part (metal equivalent) per part of 2-(3-halogeno-4-alkoxyphenyl)-2-methylpropyl chloride,
Preferably 0.0001-0.2 parts, if a solvent is required
0.1 to 30 parts of solvent are used, preferably 1.0 to 10 parts. If the amount used is large, productivity will decrease. The base is used in an amount of 0.5 to 10 equivalents, preferably 1.0 to 2.0 equivalents, per equivalent of 2-(3-halogeno-4-alkoxyphenyl)-2-methylpropyl chloride.
本発明の製造方法の一般的な実施態様は次の通
りである。 A general embodiment of the manufacturing method of the present invention is as follows.
２−（３−ハロゲノ−４−アルコキシフエニル）
−２−メチルプロピルクロリド類、接触還元触
媒、塩基、必要な場合はさらに溶媒を反応器に装
入し、水素を常圧ないし150Kg／cm2Ｇの所定圧に
して、所定温度に加熱または冷却し、所定温度で
所定時間かきまぜる。反応終了後、反応混合物を
ろ過し、溶媒を留去する。そのまま次の反応に供
し得るが、必要ならば、蒸留、カラムクロマトブ
ラフイーなどにより精製する。 2-(3-halogeno-4-alkoxyphenyl)
-2-Methylpropyl chlorides, a catalytic reduction catalyst, a base, and if necessary a solvent are charged into the reactor, hydrogen is brought to a predetermined pressure of normal pressure to 150 kg/cm 2 G, and heated or cooled to a predetermined temperature. and stir at the specified temperature for the specified time. After the reaction is completed, the reaction mixture is filtered and the solvent is distilled off. It can be used as is for the next reaction, but if necessary, it can be purified by distillation, column chromatography, etc.
実施例 １
２−（３−クロロ−４−エトキシフエニル）−２
−メチルプロピルクロリド500ｇ、５％Pd−Ｃ
（50％含水品）0.4ｇ、酢酸ナトリウム（無水）
1.65ｇ酢酸エチル25ｇを200mlオートクレーブに
装入し、オートクレーブ内を窒素置換後、水素置
換し、水素で25Kg／cm2Ｇに加圧し、かきまぜなが
ら40℃まで加熱する。その後同温で４時間かきま
ぜた。反応終了後、反応混合物をろ過した後、ろ
残を酢酸エチルで洗浄した。ろ液および洗液より
溶媒を留去して粗２−（４−エトキシフエニル）−
２−メチルプロピルクロリド4.69ｇを得た。取得
物をガスクロマトグラフイーにより分析の結果２
−（４−エトキシフエニル）−２−メチルプロピル
クロリドが81.9％含まれていた。Example 1 2-(3-chloro-4-ethoxyphenyl)-2
-Methylpropyl chloride 500g, 5% Pd-C
(50% water content) 0.4g, sodium acetate (anhydrous)
Charge 25 g of ethyl acetate (1.65 g) into a 200 ml autoclave, replace the inside of the autoclave with nitrogen and then with hydrogen, pressurize with hydrogen to 25 Kg/cm 2 G, and heat to 40°C while stirring. Thereafter, the mixture was stirred at the same temperature for 4 hours. After the reaction was completed, the reaction mixture was filtered, and the filter residue was washed with ethyl acetate. The solvent was distilled off from the filtrate and washing liquid to obtain crude 2-(4-ethoxyphenyl)-
4.69 g of 2-methylpropyl chloride was obtained. Results of analysis of the obtained material by gas chromatography 2
It contained 81.9% -(4-ethoxyphenyl)-2-methylpropyl chloride.
収率91.1％
実施例 ２
２−（３−クロロ−４−エトキシフエニル）−２
−メチル−プロピルクロリド5.00ｇ、５％Pd−Ｃ
（50％含水品）0.5ｇ、水酸化ナトリウム0.83ｇ、
酢酸ｎ−ブチル25ｇを200mlオートクレーブに装
入し、オートクレーブ内を窒素置換後、水素置換
し、水素で25Kg／cm2Ｇに加圧し、かきまぜながら
60℃まで加熱する。その後同温度で４時間かきま
ぜた。反応終了後、反応混合物をろ過した後、ろ
残をベンゼンで洗浄した。ろ液および洗液より溶
媒を留去して粗２−（４−エトキシフエニル）−２
−メチルプロピルクロリド4.82ｇを得た。取得物
をガスクロマトグラフイーにより分析の結果２−
（４−エトキシフエニル）−２−メチルプロピルク
ロリドが65.1％含まれていた。収率74.4％
実施例 ３
２−（３−クロロ−４−エトキシフエニル）−２
−メチルプロピルクロリド7.50ｇ、５％Pd−Ｃ
（50％含水品）0.75ｇ、水酸化ナトリウム1.28ｇ、
Ｎ，Ｎ−ジメチルイミダゾリジノン30ｇを200ml
オートクレーブに装入し、オートクレーブ内を窒
素置換後、水素置換し、水素で25Kg／cm2Ｇに加圧
し、かきまぜながら60℃まで加熱する。その後同
温度で８時間かきまぜた。反応終了後、反応混合
物に約150mlの水を加え、ベンゼンで抽出した。
ベンゼン層を、水洗、乾燥した後溶媒を留去して
粗２−（４−エトキシフエニル）−２−メチルプロ
ピルクロリド4.93ｇを得た。取得物をガスクロマ
トグラフイーにより分析の結果、２−（４−エト
キシフエニル）−２−メチルプロピルクロリド
66.5％含まれていた。収率76.2％
実施例 ４
原料に２−（３−クロロ−４−メトキシフエニ
ル）−２−メチルプロピルクロリド4.71ｇを使用
した他は実施例１と同様に行なつた。Yield 91.1% Example 2 2-(3-chloro-4-ethoxyphenyl)-2
-Methyl-propyl chloride 5.00g, 5% Pd-C
(50% water content) 0.5g, sodium hydroxide 0.83g,
Charge 25g of n-butyl acetate into a 200ml autoclave, replace the inside of the autoclave with nitrogen, then with hydrogen, pressurize with hydrogen to 25Kg/cm 2 G, and while stirring.
Heat to 60℃. Thereafter, the mixture was stirred at the same temperature for 4 hours. After the reaction was completed, the reaction mixture was filtered, and the filter residue was washed with benzene. The solvent was distilled off from the filtrate and washing liquid to obtain crude 2-(4-ethoxyphenyl)-2.
-4.82 g of methylpropyl chloride was obtained. Results of analysis of the obtained material by gas chromatography 2-
It contained 65.1% (4-ethoxyphenyl)-2-methylpropyl chloride. Yield 74.4% Example 3 2-(3-chloro-4-ethoxyphenyl)-2
-Methylpropyl chloride 7.50g, 5% Pd-C
(50% water content) 0.75g, sodium hydroxide 1.28g,
200ml of 30g of N,N-dimethylimidazolidinone
The autoclave is charged, the interior of the autoclave is purged with nitrogen and then with hydrogen, pressurized with hydrogen to 25 kg/cm 2 G, and heated to 60°C while stirring. Thereafter, the mixture was stirred at the same temperature for 8 hours. After the reaction was completed, about 150 ml of water was added to the reaction mixture, and the mixture was extracted with benzene.
The benzene layer was washed with water, dried, and the solvent was distilled off to obtain 4.93 g of crude 2-(4-ethoxyphenyl)-2-methylpropyl chloride. Analysis of the obtained material by gas chromatography revealed that 2-(4-ethoxyphenyl)-2-methylpropyl chloride
It contained 66.5%. Yield: 76.2% Example 4 The same procedure as in Example 1 was conducted except that 4.71 g of 2-(3-chloro-4-methoxyphenyl)-2-methylpropyl chloride was used as the raw material.
その結果粗２−（４−メトキシフエニル）−２−
メチルプロピルクロリド4.48ｇを得た。取得物を
ガスクロマトグラフイーにより分析の結果、２−
（４−メトキシフエニル）−２−メチルプロピルク
ロリドが80.2％含まれていた。 As a result, crude 2-(4-methoxyphenyl)-2-
4.48 g of methylpropyl chloride was obtained. As a result of analyzing the obtained material by gas chromatography, 2-
It contained 80.2% (4-methoxyphenyl)-2-methylpropyl chloride.
収率91.4％
実施例 ５
２−（３−クロロ−４−エシキシフエニル）−２
−メチルプロピルクロリド5.00ｇ、酸化白金0.05
ｇ、酢酸ナトリウム（無水）1.65ｇ、エタノール
25ｇを200mlオートクレーブに装入し、オートク
レーブ内を窒素置換後、水素置換し、水素で30
Kg／cm2Ｇに加圧し、かきまぜながら80℃まで加熱
する。その後同温度で４時間かきまぜた。反応終
了後、反応混合物をろ過した後、ろ液を濃縮し、
油状物4.72ｇを得た。この油状物をガスクロマト
グラフイーにより分析の結果２−（４−エトキシ
フエニル）−２−メチルプロピルクロリドが67.2
％含まれていた。収率73.7％
実施例 ６
２−（３−クロロ−４−エシキシフエニル）−２
−メチルプロピルクロリド5.00ｇ、ラネーニツケ
ル0.10ｇ、酢酸ナトリウム（無水）1.65ｇ、酢酸
エチル25ｇを200mlオートクレーブに装入し、オ
ートクレーブ内を窒素置換後、水素置換し、水素
で30Kg／cm2Ｇに加圧し、かきまぜながら90℃まで
加熱する。その後同温度で４時間かきまぜた。反
応終了後、反応混合物をろ過した後、ろ液を濃縮
し、油状物4.68ｇを得た。この油状物をガスクロ
マトグラフイーにより分析の結果２−（４−エト
キシフエニル）−２−メチルプロピルクロリドが
75.2％含まれていた。収率81.8％Yield 91.4% Example 5 2-(3-chloro-4-ethyxphenyl)-2
- Methylpropyl chloride 5.00g, platinum oxide 0.05g
g, sodium acetate (anhydrous) 1.65 g, ethanol
Charge 25g into a 200ml autoclave, replace the inside of the autoclave with nitrogen, then replace with hydrogen, and boil for 30 minutes with hydrogen.
Pressurize to Kg/cm 2 G and heat to 80℃ while stirring. Thereafter, the mixture was stirred at the same temperature for 4 hours. After the reaction is completed, the reaction mixture is filtered, and the filtrate is concentrated.
4.72 g of oil was obtained. Analysis of this oil by gas chromatography revealed 67.2% of 2-(4-ethoxyphenyl)-2-methylpropyl chloride.
% was included. Yield 73.7% Example 6 2-(3-chloro-4-ethoxyphenyl)-2
- Charge 5.00 g of methylpropyl chloride, 0.10 g of Raney nickel, 1.65 g of sodium acetate (anhydrous), and 25 g of ethyl acetate into a 200 ml autoclave, replace the inside of the autoclave with nitrogen, then replace with hydrogen, and add to 30 kg/cm 2 G with hydrogen. Press down and heat to 90℃ while stirring. Thereafter, the mixture was stirred at the same temperature for 4 hours. After the reaction was completed, the reaction mixture was filtered, and the filtrate was concentrated to obtain 4.68 g of an oily substance. Analysis of this oil by gas chromatography revealed 2-(4-ethoxyphenyl)-2-methylpropyl chloride.
It contained 75.2%. Yield 81.8%
Claims (1)
Ｘは塩素原子、臭素原子を表わす）で表わされる
２−（３−ハロゲノ−４−アルコキシフエニル）−
２−メチルプロピルクロリド類を、塩基の存在
下、パラジウム触媒、白金触媒あるいはニツケル
触媒の存在下、接触還元により脱ハロゲン化する
ことを特徴とする一般式（）； 式（）中、Ｒは前記の意味を表わす）で表わ
される２−（４−アルコキシフエニル）−２−メチ
ルプロピルクロリド類の製造法。 ２ 接触還元をパラジウム触媒の存在下に行うこ
とを特徴とする前記特許請求の範囲第１項記載の
製造法。 ３ パラジウム触媒がパラジウムカーボンである
ことを特徴とする前記特許請求の範囲第２項記載
の製造法。 ４ 一般式（）において、Ｒがメチル基、また
はエチル基であることを特徴とする前記特許請求
の範囲第１項、第２項または第３項記載の製造
法。[Claims] 1 General formula () (In formula (), R represents a lower alkyl group,
2-(3-halogeno-4-alkoxyphenyl)- represented by
General formula () characterized in that 2-methylpropyl chloride is dehalogenated by catalytic reduction in the presence of a base, a palladium catalyst, a platinum catalyst, or a nickel catalyst; A method for producing 2-(4-alkoxyphenyl)-2-methylpropyl chloride represented by the formula (in which R represents the above meaning). 2. The production method according to claim 1, wherein the catalytic reduction is carried out in the presence of a palladium catalyst. 3. The manufacturing method according to claim 2, wherein the palladium catalyst is palladium carbon. 4. The manufacturing method according to claim 1, 2 or 3, wherein in the general formula (), R is a methyl group or an ethyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59005525A JPS60149540A (en) | 1984-01-18 | 1984-01-18 | Production of 2-(4-alkoxyphenyl)-2-methylpropyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59005525A JPS60149540A (en) | 1984-01-18 | 1984-01-18 | Production of 2-(4-alkoxyphenyl)-2-methylpropyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60149540A JPS60149540A (en) | 1985-08-07 |
| JPH0557975B2 true JPH0557975B2 (en) | 1993-08-25 |
Family
ID=11613600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59005525A Granted JPS60149540A (en) | 1984-01-18 | 1984-01-18 | Production of 2-(4-alkoxyphenyl)-2-methylpropyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60149540A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5804664A (en) * | 1997-05-23 | 1998-09-08 | Kennedy; Joseph P. | Star polymers having multiple arms emanating from a calixarene core, initiators therefor, and method for the synthesis thereof |
| US5844056A (en) * | 1996-08-07 | 1998-12-01 | The University Of Akron | Star polymers having multiple polyisobutylene arms emanating from a calixarene core, initiators therefor, and method for the synthesis thereof |
| JP4948058B2 (en) * | 2006-07-04 | 2012-06-06 | カヤバ工業株式会社 | Seal structure |
-
1984
- 1984-01-18 JP JP59005525A patent/JPS60149540A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60149540A (en) | 1985-08-07 |
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